CN103088078A - Lipase synthesis-promoting method of propyl caffeate - Google Patents
Lipase synthesis-promoting method of propyl caffeate Download PDFInfo
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- CN103088078A CN103088078A CN2013100433107A CN201310043310A CN103088078A CN 103088078 A CN103088078 A CN 103088078A CN 2013100433107 A CN2013100433107 A CN 2013100433107A CN 201310043310 A CN201310043310 A CN 201310043310A CN 103088078 A CN103088078 A CN 103088078A
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- coffic acid
- lipase
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- caffeate
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Abstract
The invention relates to a lipase synthesis-promoting method of propyl caffeate. The method comprises the steps that: an ionic liquid is adopted as a reaction medium, lipase is adopted as a catalyst, and the propyl caffeate is prepared through a reaction of caffeic acid or alkyl caffeate and propanol in the reaction medium. The molar ratio of caffeic acid or alkyl caffeate to propanol is 1:(5-100), a reaction temperature is 40-80 DEG C, a reaction time is 10-72h, a mass ratio of caffeic acid or alkyl caffeate to lipase is 1:(1-25), and a mass-volume ratio of caffeic acid or alkyl caffeate in the ionic liquid is (1-30):1. The method has the advantages of mild reaction conditions and environment friendliness. With the method, a defect of low solubility of catalytic synthesis substrate in a traditional method in which an organic solvent is adopted as a reaction medium is overcome; and high-purity propyl caffeate can easily be obtained.
Description
Technical field
The present invention relates to biocatalysis field, be specifically related to a kind of fatty enzymatic synthesis method of coffic acid propyl ester.
Background technology
Prior art: coffic acid propyl ester, English name: Caffeic acid propyl ester, chemical name: (E)-propyl group-3-(3,4-dihydroxyl) acrylate, molecular formula: C
11H
12O
4, molecular weight: 208.16, chemical structure is as shown in Figure 1.
Coffic acid and its derivative extensively are distributed in the tissue of many plants, comprise coffee, fruit, vegetables and tobacco refuse (Journal of Chromatography A, 2005,1098 (1 – 2): 66-74), be the effective constituent of numerous medicinal materials and Chinese patent medicine antibacterial and detoxicating, anti-inflammatory and choleretic, have strong anti-oxidation (Fitoterapia, 2002,73, Supplement1 (0): S21-S29) and antitumour activity (Bioorganic﹠amp; Medicinal Chemistry, 2008,16 (16): 7795-7803), the pharmacological action such as hypotensive, germ resistance, antiviral, anti-inflammatory in addition.In recent years, coffic acid and derivative thereof are extensively applied in food, health care, makeup and pharmaceutical industry.But because coffic acid is water-soluble strong, fat-soluble poor, can't directly apply in the higher food of fat content.Generally speaking, can improve by the method for esterification the fat-soluble of compound.In early-stage Study, we find with respect to other coffic acid alkyl esters, and the coffic acid propyl ester has the strongest anti-oxidant activity.
The coffic acid propyl ester preparation method who has reported is all take organic solvent as reaction medium, take traditional acid as catalyzer, adopt the esterification synthetic method, have byproduct of reaction too much, shortcoming (the Journal ofMolecular catalysisA:chemical such as traditional catalyst is strong to the corrodibility of equipment, the product separation process is too complicated and volatile organic solvent gas environmental pollution is larger, 2005,234:107-110).Therefore, be badly in need of seeking a kind of novel, green reaction medium and catalyzer solves above technological deficiency.
Summary of the invention
The technical problem that solves: for solving above defective, the present invention is intended to set up take ionic liquid as reaction medium, prepares the coffic acid propyl ester take lipase as catalyzer by direct esterification and ester exchange method.The method is easy and simple to handle, reaction conditions is gentle, efficiency of pcr product is high, environmentally friendly, thereby can overcome traditional lipase-catalyzed synthesis efficient hangs down and the lower shortcoming of substrate solubleness, be easy to production high purity coffic acid propyl ester, be of great significance for promoting its widespread use tool in the industry such as medicine, food.
Technical scheme:
The fatty enzymatic synthesis method of coffic acid propyl ester, its structural formula is as follows, and preparation process is:
Take ionic liquid as reaction medium, lipase is catalyzer, adopt the synthetic coffic acid propyl ester of coffic acid or coffic acid alkyl ester and propyl alcohol reaction, the mol ratio of described coffic acid or coffic acid alkyl ester and propyl alcohol is 1:(5 ~ 100), temperature of reaction is 40 ~ 80 ℃, reaction times is 10 ~ 72h, and the mass ratio of coffic acid or coffic acid alkyl ester and lipase is 1:(1 ~ 25), coffic acid or the coffic acid alkyl ester mass volume ratio (g/mL) in ionic liquid is (1 ~ 30): 1.
Preferably, add ionic liquid in sealed vessel, then add coffic acid or coffic acid alkyl ester, propyl alcohol and lipase, the heating oscillatory reaction obtains the coffic acid propyl ester.
Described coffic acid alkyl ester is Methyl caffeoate or NSC 619661.
Described ionic liquid is [Bmim] [Tf
2N], [Hmim] [HSO
4], [Bmim] [PF
6], [Hmim] [Cl], [Emim] [CF
3OAC], [Emim] [OTf], [Nmim] [HSO
4], [Omim] [BF
4], [TOMA] [Tf
2N], [Nmim] [Cl], [Emim] [Tf
2N], [Bmim] [CF
3SO
3] or [Bmim] [Bf
4].
Described lipase is Novozym435, Lipozyme RM IM or Lipozyme TL RM.
Beneficial effect:
Select suitable ionic liquid to strengthen combined coefficient as reaction medium in the system of the synthetic coffic acid propyl ester of enzymatic, the method reaction conditions is gentle, environmentally friendly, overcome traditional lower shortcoming of substrate solubleness that catalyzes and synthesizes take organic solvent as reaction medium, be easy to production high purity coffic acid propyl ester, purity 94.36% is through purity 98.5% after recrystallization.In addition, the essentially no generation of waste materials of whole enzymatic reaction technique, non-environmental-pollution has very good industrial applications prospect, can satisfy the needs of the grocery trade that develops rapidly.
Description of drawings
Fig. 1 is reaction formula of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The high-efficient liquid phase chromatogram condition that detects the coffic acid propyl ester is: the AlltimaTM C18 post that adopts 250mm * 4.6mm, moving phase is methyl alcohol: water (V:V)=65:35, flow velocity are 1mL/min, and column temperature is 30 ℃, the detection wavelength is 325nm, and sample size is 20 μ L.
Wherein, the yield method of calculation of product coffic acid propyl ester are:
Embodiment 1
The process of catalyst esterification is made in the present embodiment explanation with lipase.
According to reaction system for adding coffic acid 0.01g, the mol ratio of coffic acid and propyl alcohol 1: 10, with the mass ratio of lipase be 1:20, then add 1mL ionic liquid [Bmim] [Tf
2N], the concussion reaction 72h that then heats up in shaking bath, temperature is controlled at 70 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and its peak area is 5324670, and the yield of coffic acid propyl ester is 41.00%, its purity is 91.86%.
Embodiment 2
The process of catalyst esterification is made in the present embodiment explanation with lipase.
According to reaction system for adding coffic acid 0.01g, the mol ratio 1:5 of coffic acid and propyl alcohol, with the mass ratio of lipase be that 1:20 adds 1mL[Hmim again] [HSO
4], the concussion reaction 48h that then heats up in shaking bath, temperature is controlled at 70 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and the yield of coffic acid propyl ester is 29.66%, and its purity is 92.62%.
Embodiment 3
The process of catalyst esterification is made in the present embodiment explanation with lipase.
Be coffic acid 0.01g according to reaction system, the mol ratio of coffic acid and propyl alcohol 1: 10, with the mass ratio of lipase be 1:20, add afterwards 1mL[Bmim] [Tf
2N], the concussion reaction 72h that then heats up in shaking bath, temperature is controlled at 80 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and the yield of coffic acid propyl ester is 30.97%, and its purity is 92.59%.
Embodiment 4
The process of catalyst transesterification reaction is made in the present embodiment explanation with lipase.
According to Methyl caffeoate 0.01g, the mol ratio of Methyl caffeoate and propyl alcohol is 1:5, with the mass ratio 1:20 of lipase, then adds 1mL ionic liquid [Bmim] [CF
3SO
3], the concussion reaction 36h that then heats up in shaking bath, temperature is controlled at 60 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and the yield of coffic acid propyl ester is 100%, and its purity is 93.29%.
Embodiment 5
The process of catalyst transesterification reaction is made in the present embodiment explanation with lipase.
According to Methyl caffeoate 0.01g, the mol ratio of Methyl caffeoate and propyl alcohol is 1:5, and the mass ratio 1:20 with lipase adds 0.2g lipase afterwards, then adds 1mL ionic liquid [Bmim] [Tf
2N], the concussion reaction 56h that then heats up in shaking bath, temperature is controlled at 70 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and the yield of coffic acid propyl ester is 24.36%, and its purity is 94.36%.
Embodiment 6
The process of catalyst transesterification reaction is made in the present embodiment explanation with lipase.
According to NSC 619661 0.01g, the mol ratio of NSC 619661 and propyl alcohol is 1: 10, with the mass ratio 1:15 of lipase, then adds 1mL ionic liquid [Bmim] [CF
3SO
3], the concussion reaction 36h that then heats up in shaking bath, temperature is controlled at 70 ℃, and the 10 μ L that then take a sample are diluted to 1mL with methyl alcohol, then carry out HPLC and detect, and the yield of coffic acid propyl ester is 17.15%, and its purity is 92.4%.
Claims (5)
1. the fatty enzymatic synthesis method of coffic acid propyl ester, its structural formula is as follows, it is characterized in that preparation process is:
Take ionic liquid as reaction medium, lipase is catalyzer, adopt the synthetic coffic acid propyl ester of coffic acid or coffic acid alkyl ester and propyl alcohol reaction, the mol ratio of described coffic acid or coffic acid alkyl ester and propyl alcohol is 1:(5 ~ 100), temperature of reaction is 40 ~ 80 ℃, reaction times is 10 ~ 72h, and the mass ratio of coffic acid or coffic acid alkyl ester and lipase is 1:(1 ~ 25), coffic acid or the coffic acid alkyl ester mass volume ratio (g/mL) in ionic liquid is (1 ~ 30): 1.
2. as the fatty enzymatic synthesis method of the coffic acid propyl ester in claim 1, it is characterized in that: add ionic liquid in sealed vessel, then add coffic acid or coffic acid alkyl ester, propyl alcohol and lipase, the heating oscillatory reaction obtains the coffic acid propyl ester.
3. as the fatty enzymatic synthesis method of the coffic acid propyl ester in claim 1, it is characterized in that: described coffic acid alkyl ester is Methyl caffeoate or NSC 619661.
4. as the fatty enzymatic synthesis method of the coffic acid propyl ester in claim 1, it is characterized in that: described ionic liquid is [Bmim] [Tf
2N], [Hmim] [HSO
4], [Bmim] [PF
6], [Hmim] [Cl], [Emim] [CF
3OAC], [Emim] [OTf], [Nmim] [HSO
4], [Omim] [BF
4], [TOMA] [Tf
2N], [Nmim] [Cl], [Emim] [Tf
2N], [Bmim] [CF
3SO
3] or [Bmim] [Bf
4].
5. as the fatty enzymatic synthesis method of the coffic acid propyl ester in claim 1, it is characterized in that: described lipase is Novozym435, Lipozyme RM IM or Lipozyme TL RM.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468754A (en) * | 2013-08-15 | 2013-12-25 | 江苏科技大学 | Method for enzymatic synthesis of propyl caffeate by utilizing microreactor |
| CN106588664A (en) * | 2016-10-26 | 2017-04-26 | 华南理工大学 | Water-soluble caffeoyl structural grease, and preparation method and application thereof |
| CN106588665A (en) * | 2016-10-26 | 2017-04-26 | 华南理工大学 | Lipid soluble caffeic acid fatty acid structure grease, preparation method and application thereof |
| CN113402392A (en) * | 2021-06-28 | 2021-09-17 | 华南理工大学 | P-coumaric acid ester and synthetic method and application thereof |
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| EP1867729A1 (en) * | 2006-06-14 | 2007-12-19 | Libragen | Water soluble phenolics derivatives with dermocosmetic and therapeutic applications |
| CN101392272A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Method for enzymatic synthesis of caffeic acid phenethyl ester by solvent-free system |
| CN102321692A (en) * | 2011-09-27 | 2012-01-18 | 江苏科技大学 | Preparation method for catalytic synthesis of caffeic acid phenethyl ester by using lipase in ionic liquid |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1867729A1 (en) * | 2006-06-14 | 2007-12-19 | Libragen | Water soluble phenolics derivatives with dermocosmetic and therapeutic applications |
| CN101392272A (en) * | 2008-11-05 | 2009-03-25 | 东华大学 | Method for enzymatic synthesis of caffeic acid phenethyl ester by solvent-free system |
| CN102321692A (en) * | 2011-09-27 | 2012-01-18 | 江苏科技大学 | Preparation method for catalytic synthesis of caffeic acid phenethyl ester by using lipase in ionic liquid |
Non-Patent Citations (2)
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| KURATA A.ET.AL: "Enzymatic synthesis of caffeic acid phenethyl ester analogues in ionic liquid", 《JOURNAL OF BIOTECHNOLOGY》 * |
| NA PANG ET.AL: "Lipase-catalyzed synthesis of caffeic acid propyl ester in Ionic liquid", 《ADVANCED MATERIAL RESEARCH》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468754A (en) * | 2013-08-15 | 2013-12-25 | 江苏科技大学 | Method for enzymatic synthesis of propyl caffeate by utilizing microreactor |
| CN106588664A (en) * | 2016-10-26 | 2017-04-26 | 华南理工大学 | Water-soluble caffeoyl structural grease, and preparation method and application thereof |
| CN106588665A (en) * | 2016-10-26 | 2017-04-26 | 华南理工大学 | Lipid soluble caffeic acid fatty acid structure grease, preparation method and application thereof |
| CN113402392A (en) * | 2021-06-28 | 2021-09-17 | 华南理工大学 | P-coumaric acid ester and synthetic method and application thereof |
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| CN103088078B (en) | 2015-07-01 |
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